Polyaniline (PANI) has been electrodeposited on iron in oxalic medium in order to evaluate the protective character of this polymer. PANI has been found to be efficient for corrosion protection during at least 10 h in a pH 4.5 sulfate medium. Interaction between the passive layer and polymer has been studied using spectroelectrochemical techniques such as Raman spectroscopy and reflectance measurements.